US3997592A - Preparation of aqueous dispersions of blocked aromatic polyisocyanates - Google Patents
Preparation of aqueous dispersions of blocked aromatic polyisocyanates Download PDFInfo
- Publication number
- US3997592A US3997592A US05/634,641 US63464175A US3997592A US 3997592 A US3997592 A US 3997592A US 63464175 A US63464175 A US 63464175A US 3997592 A US3997592 A US 3997592A
- Authority
- US
- United States
- Prior art keywords
- phenolic compound
- resorcinol
- present
- polyisocyanate
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 24
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 24
- 239000006185 dispersion Substances 0.000 title claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title description 3
- 150000002989 phenols Chemical class 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 150000002513 isocyanates Chemical class 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- -1 phenol compound Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- FDAJTLLBHNHECW-UHFFFAOYSA-N 2,4-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=C(O)C(CCCCCCCCC)=C1 FDAJTLLBHNHECW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- XJOMRMNFQMEQBA-UHFFFAOYSA-N N=C=O.OC1=CC=CC(O)=C1 Chemical compound N=C=O.OC1=CC=CC(O)=C1 XJOMRMNFQMEQBA-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- LFIBXYWRWSYUFE-UHFFFAOYSA-L disodium;2-decyl-3,3-dioctyl-2-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCCCC(C([O-])=O)(S(O)(=O)=O)C(CCCCCCCC)(CCCCCCCC)C([O-])=O LFIBXYWRWSYUFE-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/16—Preparation of derivatives of isocyanic acid by reactions not involving the formation of isocyanate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
- C08G18/8019—Masked aromatic polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
- C08G18/8067—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds phenolic compounds
Abstract
Aqueous dispersions of aromatic polyisocyanates blocked with phenolic compounds are prepared by mixing the polyisocyanate and an aqueous solution containing an excess of the phenolic compound in the presence of a basic catalyst at a temperature above the melting point of the polyisocyanate.
Description
This invention relates to a process for the preparation of aqueous dispersions of aromatic polyisocyanates blocked with phenolic compounds. Such dispersions are suitable for use in the formation of a single dip coating on polyester substrates and such coatings cause the polyester to adhere to rubber.
It is known to prepare phenol blocked aromatic polyisocyanates by reacting the components in an organic solvent. It is also known to form aqueous dispersions of blocked isocyanates by mixing an aqueous solution of phenol and a solution of a polyisocyanate dissolved in a water soluble organic solvent. The present invention directly produces an aqueous dispersion of a blocked polyisocyanate without the use of an organic solvent.
The present invention comprises a process for the preparation of an aqueous dispersion of a phenolic compound-blocked aromatic polyisocyanate. This aqueous dispersion is obtained by intimately mixing an aromatic polyisocyanate and an aqueous solution of a phenolic compound in the presence of an effective amount of a basic catalyst at a temperature above the melting point of the polyisocyanate. A preferred temperature range is from 25° to 90° C. The reaction rate is temperature dependent, but the reaction will be substantially complete in from 2 to 60 minutes. In the preferred process the polyisocyanate is added to the solution of the phenolic compound.
The number of moles of the phenolic compound employed should be at least equal to the number of equivalents of isocyanate groups present, and the number of moles of phenolic compound may be as much as 8 times the number of equivalents of isocyanate groups. The preferred range of moles of phenolic compound per equivalent isocyanate group is about 1.01 to about 5.
An effective amount of basic catalyst is usually about 0.01 to 1 wt. percent based on the amount of water present. Suitable bases include any alkali metal hydroxide, tertiary aliphatic amines such as triethyl amine, diethyl cyclohexyl amine, and guanidines such as tetramethylguanidine.
The phenolic compound employed as the blocking agent can be phenol, resorcinol, C1 to C15 alkyl derivatives of phenol and C1 to C15 derivatives of resorcinol.
Aromatic polyisocyanates are a well known class of compounds, and any of these compounds may be used herein, but the preferred compounds are 4,4'-methylene diphenylisocyanate, toluene-2,4-diisocyanate, benzene-1,3-diisocyanate, diphenylether-2,4,4'-triisocyanate, and triphenylmethane-4,4',4"-triiisocyanate. 4,4'-Methylene diphenylisocyanate is the preferred compound.
It is desirable when carrying out the blocking reaction to have present in the mixture a surfactant. Suitable surfactants may be either anionic or nonionic. Suitable anionic surfactants are sodium dioctylsulfosuccinate and sodium dioctyldecylsulfosuccinate. Suitable nonionic surfactants include the olefin/vinyl pyrrolidone copolymers, sold commercially as "Ganex" V polymers. U.S. Pat. No. 3,591,568 to Farber describes these materials in more detail. The surfactant can be present in the reaction mixture in the amount of about 1-10% by weight of the blocked isocyanate.
Since the mixing of the aromatic polyisocyanate and the aqueous solution of a phenol compound takes place under conditions such that the polyisocyanate is in the liquid state, that is, at a temperature above the melting point of the polyisocyanate, it is usually preferred to have the temperature of both the aqueous solution of the phenol compound and the aromatic polyisocyanate above the melting point of the polyisocyanate. Since it is usually preferred to add the aromatic isocyanate to the aqueous solution, the temperature of the aqueous solution should preferably be at least about 1° to 5° C. above the melting point of the aromatic polyisocyanate.
It is highly desirable that the mixing of the ingredients be carried out quickly and efficiently. High speed mixers available commercially are satisfactory to achieve the desired good agitation and intimate mixture.
The particle size of the precipitate formed can be regulated by addition of greater or lesser amounts of surfactants and by agitation rate.
The dispersions formed by the present invention may be used to form single dip coating solutions for polyesters. If the phenolic compound employed in the formation of the dispersion is resorcinol, an aqueous solution of formaldehyde is merely added with mixing to the dispersion; a resorcinol-formaldehyde resin thus directly forms as the resorcinol was added in excess of that needed to block the isocyanate. On the other hand, if phenol is employed in blocking the isocyanate, then an amount of resorcinol is first added to the dispersion such that in the final dispersion the weight ratio of resorcinol-formaldehyde resin to blocked aromatic polyisocyanate is in the range of about 0.2 to 1 to about 1.5 to 1.
The formation of the resorcinol-formaldehyde resin in the dispersion of blocked isocyanate takes place on the addition of formaldehyde to the dispersion containing the resorcinol. This reaction is best carried out at a temperature in the range of about 25° to 50° C. The resorcinol is preferably present in a small molar excess over the amount of formaldehyde present.
The final coating solution must also contain a water insoluble polyepoxide and a rubber latex. These components are merely added in accordance with the conventional practices of the art as illustrated by U.S. Pat. No. 3,234,067. The weight ratio of polyepoxide present in the dispersion to amount of blocked isocyanate present should be about 0.1 to 1 to about 4 to 1. The amount of rubber latex solids present in the dispersion should be from about equal to the amount of resorcinol-formaldehyde resin present to about 6 times the amount of resorcinol-formaldehyde resin present.
The coating solution will contain about 6 to 24% by weight total solids. It may be applied in the conventional manner to the polyester substrate. After application the coating is heated to above about 200° C. for 0.5 to 15 minutes to remove the water and cure the coating. Usually the polyester substrate is kept under tension to prevent shrinkage. Thereafter rubber is applied and cured.
The single dip coating composition contains about 0.01 to 1 wt. percent alkali metal hydroxide, based on the weight of the water present.
In the examples which follow, all parts and percentages are in parts by weight and all temperatures are in degrees centigrade unless otherwise specified.
A 5-liter round-bottom flask was charged with 400 g resorcinol, 1800 ml. water, 3.0 g sodium hydroxide pellets, 30 g sodium dioctylsulfosuccinate (100% active, sold as Aerosol OT by American Cyanamid), and a droplet of silicon complex antifoaming agent (sold as Dow "Antifoam" C by Dow Chemical Co.). The mixture became homogeneous while being warmed to 45° C. with stirring. To the warm vigorously agitated solution was added 200 g molten 4,4'-methylene diphenylisocyanate at about 45° C. Addition was completed in one minute. A precipitate appeared and the temperature rose to a peak of 52° C. after eight minutes and then began to subside. After about an hour the reaction mixture was cooled and the precipitate collected by suction filtration. The cake of precipitate was washed with water, air dried, and then dried in a vacuum desiccator to yield a white powder weighing 362 g. The product was identified as the bis resorcinol adduct of the isocyanate (94% pure) by its infrared spectrum, melting point, nitrogen analysis and solubility in acetone. The product contained about 5% of a resorcinol-isocyanate polymer, and less than 1% of an isocyanate-based polyurea.
A solution of 390 g resorcinol, 27.3 g nonylphenol (principally p-nonylphenol with about 3% ortho isomer and 4% 2,4-dinonylphenol sold by Rohm and Haas Co.), 30.9 g sodium dioctyl sulfosuccinate (75% active, sold as Aerosol OT by American Cyanamid), 58.5 ml 5% solution hydroxide solution, and a drop of Dow Antifoam C in 1700 ml. deaerated water was prepared under nitrogen in a 5-liter roundbottom flask. The solution was warmed to about 48° C. and poured into a 4-liter steel beaker into which an Eppenbach Homomixer was inserted. Through a dip leg leading to the base of the Homomixer was added 195 g molten 4,4'-methylene diphenylisocyanate (at about 45° C.) while the mixer was operating at about 80% of maximum speed. Addition was completed in less than one minute. A milky white dispersion formed immediately, and the temperature rose rapidly to about 58° C., then started to fall. The dispersion was cooled to 25° C. and 600 g were filtered as described in Example 1. The product was isolated in 96.5% yield and consisted of 95.9% of a mixture of the resorcinol and nonylphenol adducts of the isocyanate.
To the remaining 1802 g of dispersion was added 77 g 37% aqueous formaldehyde and the mixture stirred one hour. The mixture was used in combination with a micronized epoxy cresol novolak resin (sold as ECN 9595 by Ciba Geigy) and a butadiene/styrene/2-vinyl pyridine latex to prepare a single dip adhesive. When tested as an adhesive for polyester tire cord in a standard rubber compound, adhesion was excellent.
To a solution of 44.6 parts of phenol and 0.04 parts of diethylcyclohexylamine in 142.3 parts of water was added 0.95 parts of an alkylated polyvinylpyrrolidone (Ganex V-220, avg. mol. wt.˜8600, sold by GAF Corp.) dissolved in 3.2 parts of n-heptane. This aqueous dispersion was heated to 65°-70° C. and 59.2 parts of 4,4'-methylene diphenylisocyanate was added over a one hour period. The reaction mass was cooled to 30 ± 5° C. and the wet product isolated by filtration. Drying to constant weight at 70°-80° C. and 25" Hg gave 100 parts dry product. Analysis showed the product to be about 90% bis phenol adduct of the isocyanate and about 10% blocked urea and biurets.
Claims (8)
1. A process for the production of an aqueous dispersion of an aromatic polyisocyanate blocked with a phenolic compound which comprises mixing (a) an aromatic polyisocyanate and (b) an aqueous solution containing a dissolved phenolic compound selected from the class consisting of phenol, resorcinol and C1 to C15 alkyl derivatives of phenol and C1 to C15 alkyl derivatives of resorcinol, at a temperature above the melting point of the polyisocyanate, in the presence of an effective amount of a basic catalyst, the number of moles of phenolic compound being at least equal to the number of equivalents of isocyanate groups present.
2. The process of claim 1 in which the mixing takes place at a temperature between about 25° and 90° C.
3. The process of claim 2 in which the basic catalyst is an alkali metal hydroxide, and the basic catalyst is present in the amount of about 0.01 to 1.0 wt. percent based on the amount of water present.
4. The process of claim 1 in which a surfactant is present in aqueous solution of phenolic compound.
5. The process of claim 4 in which the surfactant is nonionic or anionic.
6. The process of claim 1 in which the aromatic polyisocyanate is selected from the class consisting of 4,4'-methylene diphenylisocyanate, toluene-2,4-diisocyanate, benzene-1,3-diisocyanate, diphenylether-2,4,4'-triisocyanate, and triphenylmethane-4,4'4"-triisocyanate.
7. The process of claim 6 in which the phenolic compound is resorcinol.
8. The process of claim 6 in which the phenolic compound is phenol.
Priority Applications (16)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/634,641 US3997592A (en) | 1975-11-24 | 1975-11-24 | Preparation of aqueous dispersions of blocked aromatic polyisocyanates |
FR7634719A FR2332294A1 (en) | 1975-11-24 | 1976-11-18 | PREPARATION OF AQUEOUS DISPERSIONS OF BLOCKED AROMATIC POLYISOCYANATES |
DE19762652839 DE2652839A1 (en) | 1975-11-24 | 1976-11-20 | PROCESS FOR THE PREPARATION OF AQUATIC DISPERSIONS OF AROMATIC POLYISOCYANATES |
CA266,218A CA1058853A (en) | 1975-11-24 | 1976-11-22 | Preparation of aqueous dispersions of blocked aromatic polyisocyanates |
JP51139643A JPS5923301B2 (en) | 1975-11-24 | 1976-11-22 | Method for producing blocked aromatic polyisocyanate aqueous dispersion |
SE7613074A SE437154B (en) | 1975-11-24 | 1976-11-23 | PROCEDURE FOR PREPARING AN Aqueous CONTENT OF AN AROMATIC POLYISOCYANATE BLOCKED WITH A PHENOLIC COMPOUND |
ES453565A ES453565A1 (en) | 1975-11-24 | 1976-11-23 | Preparation of aqueous dispersions of blocked aromatic polyisocyanates |
GB48828/76A GB1550489A (en) | 1975-11-24 | 1976-11-23 | Preparation of aqueous dispersions of aromatic polyisocyanates blocked by phenols and their use for the formation of single dip coatings on polyester substrates |
DK526776A DK526776A (en) | 1975-11-24 | 1976-11-23 | PROCEDURE FOR PREPARING AN AQUATIC DISPERSION OF AN AROMATIC POLYISOCYANATE BLOCKED WITH PHENOLIC COMPOUND |
BR7607847A BR7607847A (en) | 1975-11-24 | 1976-11-23 | PROCESS FOR THE PRODUCTION OF A WATER DISPRESSION OF AN AROMATIC POLYISOCIANATE BLOCKED WITH A PHENOLIC COMPOUND |
AU19896/76A AU501096B2 (en) | 1975-11-24 | 1976-11-23 | Aqueous dispersions of blocked aromatic polyisocyanates |
BE172611A BE848648A (en) | 1975-11-24 | 1976-11-23 | PREPARATION OF AQUEOUS DISPERSIONS OF BLOCKED AROMATIC POLYISOCYANATES, |
IE2580/76A IE43989B1 (en) | 1975-11-24 | 1976-11-24 | Preparation of aqueous dispersions of aromatic polyisocyanates blockes by phenols and their use for the formation of single dip coating on polyester substrates |
LU76258A LU76258A1 (en) | 1975-11-24 | 1976-11-24 | |
NL7613105A NL7613105A (en) | 1975-11-24 | 1976-11-24 | PROCESS FOR PREPARING A HYDROGEN DISPERSION OF MASKED AROMATIC POLYISOCYANATE. |
IT29720/76A IT1064475B (en) | 1975-11-24 | 1976-11-24 | METHOD FOR PREPARING BLOCKED AROMATIC POLYISOCYANATE WATER DISPERSIONS |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/634,641 US3997592A (en) | 1975-11-24 | 1975-11-24 | Preparation of aqueous dispersions of blocked aromatic polyisocyanates |
Publications (1)
Publication Number | Publication Date |
---|---|
US3997592A true US3997592A (en) | 1976-12-14 |
Family
ID=24544638
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/634,641 Expired - Lifetime US3997592A (en) | 1975-11-24 | 1975-11-24 | Preparation of aqueous dispersions of blocked aromatic polyisocyanates |
Country Status (16)
Country | Link |
---|---|
US (1) | US3997592A (en) |
JP (1) | JPS5923301B2 (en) |
AU (1) | AU501096B2 (en) |
BE (1) | BE848648A (en) |
BR (1) | BR7607847A (en) |
CA (1) | CA1058853A (en) |
DE (1) | DE2652839A1 (en) |
DK (1) | DK526776A (en) |
ES (1) | ES453565A1 (en) |
FR (1) | FR2332294A1 (en) |
GB (1) | GB1550489A (en) |
IE (1) | IE43989B1 (en) |
IT (1) | IT1064475B (en) |
LU (1) | LU76258A1 (en) |
NL (1) | NL7613105A (en) |
SE (1) | SE437154B (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4280944A (en) * | 1979-05-17 | 1981-07-28 | Mitsui-Nisso Corporation | Thermosetting polyurethane resin and coating agent thereof prepared from at least two polyoxyalkylene polyols, blocking agent, chain-elongating agent, cross-linking agent and a mixture of diisocyanates |
EP0072483A1 (en) * | 1981-08-14 | 1983-02-23 | Mobay Chemical Corporation | Self-granulating reaction product of 4,4'-diphenylmethane diisocyanate and resorcinol |
US4477619A (en) * | 1982-10-08 | 1984-10-16 | The B. F. Goodrich Company | Preparation of fabric for bonding to rubber |
US4720398A (en) * | 1984-03-19 | 1988-01-19 | Akzo Nv | Process for the improvement of the adhesion to rubber or a thermoplastic elastomer of synthetic yarns, cords or fabrics made therefrom |
US4723032A (en) * | 1981-11-12 | 1988-02-02 | Bayer Aktiengesellschaft | Modified polyamines and a process for their production |
US4816597A (en) * | 1983-10-02 | 1989-03-28 | New Jersey Institute Of Technology | Dental restorative materials based upon blocked isocyanates |
US5296160A (en) * | 1991-07-23 | 1994-03-22 | Miles Inc. | Aqueous dispersions of blocked polyisocyanates |
US6316108B1 (en) | 1998-04-01 | 2001-11-13 | The Dow Chemical Company | Process for coating substrates having polar surfaces with polyurethane latexes |
US6451908B1 (en) | 1999-04-14 | 2002-09-17 | The Dow Chemical Company | Polyurethane films prepared from polyurethane dispersions |
US6514572B1 (en) | 1999-04-14 | 2003-02-04 | Dow Global Technologies Inc. | Polyurethane films prepared by electrodeposition from polyurethane dispersions |
US6720385B2 (en) | 1997-03-17 | 2004-04-13 | The Dow Chemical Company | Polyurethane latexes, processes for preparing them and polymers prepared therewith |
US20070205393A1 (en) * | 2006-03-03 | 2007-09-06 | Indspec Chemical Corporation | Resorcinol-Blocked Isocyanate Compositions and Their Applications |
US20070219306A1 (en) * | 2006-03-03 | 2007-09-20 | Indspec Chemical Corporation | Resorcinol Resin-Blocked Isocyanates and Their Applications |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3268467A (en) * | 1961-11-03 | 1966-08-23 | Goodyear Tire & Rubber | Adhesive composition comprising the reaction product of polyisocyanate and a formaldehyde condensate |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1269642A (en) * | 1968-07-08 | 1972-04-06 | Ici Ltd | Manufacture of isocyanate reaction products |
US3933677A (en) * | 1974-05-24 | 1976-01-20 | E. I. Du Pont De Nemours & Company | Preparation of aqueous dispersions of blocked aromatic polyisocyanates |
US3963710A (en) * | 1974-08-28 | 1976-06-15 | E. I. Du Pont De Nemours And Company | Finely divided blocked isocyanates prepared in the presence of surfactants |
-
1975
- 1975-11-24 US US05/634,641 patent/US3997592A/en not_active Expired - Lifetime
-
1976
- 1976-11-18 FR FR7634719A patent/FR2332294A1/en active Granted
- 1976-11-20 DE DE19762652839 patent/DE2652839A1/en not_active Withdrawn
- 1976-11-22 CA CA266,218A patent/CA1058853A/en not_active Expired
- 1976-11-22 JP JP51139643A patent/JPS5923301B2/en not_active Expired
- 1976-11-23 GB GB48828/76A patent/GB1550489A/en not_active Expired
- 1976-11-23 AU AU19896/76A patent/AU501096B2/en not_active Expired
- 1976-11-23 SE SE7613074A patent/SE437154B/en unknown
- 1976-11-23 ES ES453565A patent/ES453565A1/en not_active Expired
- 1976-11-23 DK DK526776A patent/DK526776A/en not_active Application Discontinuation
- 1976-11-23 BR BR7607847A patent/BR7607847A/en unknown
- 1976-11-23 BE BE172611A patent/BE848648A/en not_active IP Right Cessation
- 1976-11-24 NL NL7613105A patent/NL7613105A/en not_active Application Discontinuation
- 1976-11-24 IT IT29720/76A patent/IT1064475B/en active
- 1976-11-24 IE IE2580/76A patent/IE43989B1/en unknown
- 1976-11-24 LU LU76258A patent/LU76258A1/xx unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3268467A (en) * | 1961-11-03 | 1966-08-23 | Goodyear Tire & Rubber | Adhesive composition comprising the reaction product of polyisocyanate and a formaldehyde condensate |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4280944A (en) * | 1979-05-17 | 1981-07-28 | Mitsui-Nisso Corporation | Thermosetting polyurethane resin and coating agent thereof prepared from at least two polyoxyalkylene polyols, blocking agent, chain-elongating agent, cross-linking agent and a mixture of diisocyanates |
EP0072483A1 (en) * | 1981-08-14 | 1983-02-23 | Mobay Chemical Corporation | Self-granulating reaction product of 4,4'-diphenylmethane diisocyanate and resorcinol |
US4723032A (en) * | 1981-11-12 | 1988-02-02 | Bayer Aktiengesellschaft | Modified polyamines and a process for their production |
US4477619A (en) * | 1982-10-08 | 1984-10-16 | The B. F. Goodrich Company | Preparation of fabric for bonding to rubber |
US4816597A (en) * | 1983-10-02 | 1989-03-28 | New Jersey Institute Of Technology | Dental restorative materials based upon blocked isocyanates |
US4720398A (en) * | 1984-03-19 | 1988-01-19 | Akzo Nv | Process for the improvement of the adhesion to rubber or a thermoplastic elastomer of synthetic yarns, cords or fabrics made therefrom |
US5296160A (en) * | 1991-07-23 | 1994-03-22 | Miles Inc. | Aqueous dispersions of blocked polyisocyanates |
US6720385B2 (en) | 1997-03-17 | 2004-04-13 | The Dow Chemical Company | Polyurethane latexes, processes for preparing them and polymers prepared therewith |
US6316108B1 (en) | 1998-04-01 | 2001-11-13 | The Dow Chemical Company | Process for coating substrates having polar surfaces with polyurethane latexes |
US6451908B1 (en) | 1999-04-14 | 2002-09-17 | The Dow Chemical Company | Polyurethane films prepared from polyurethane dispersions |
US6514572B1 (en) | 1999-04-14 | 2003-02-04 | Dow Global Technologies Inc. | Polyurethane films prepared by electrodeposition from polyurethane dispersions |
US20070205393A1 (en) * | 2006-03-03 | 2007-09-06 | Indspec Chemical Corporation | Resorcinol-Blocked Isocyanate Compositions and Their Applications |
US20070219306A1 (en) * | 2006-03-03 | 2007-09-20 | Indspec Chemical Corporation | Resorcinol Resin-Blocked Isocyanates and Their Applications |
US7700687B2 (en) | 2006-03-03 | 2010-04-20 | Indspec Chemical Corporation | Resorcinol resin-blocked isocyanates and their applications |
US7705088B2 (en) | 2006-03-03 | 2010-04-27 | Indspec Chemical Corporation | Resorcinol-blocked isocyanate compositions and their applications |
Also Published As
Publication number | Publication date |
---|---|
NL7613105A (en) | 1977-05-26 |
BE848648A (en) | 1977-05-23 |
LU76258A1 (en) | 1977-06-07 |
GB1550489A (en) | 1979-08-15 |
DE2652839A1 (en) | 1977-05-26 |
SE7613074L (en) | 1977-05-25 |
IE43989B1 (en) | 1981-07-15 |
DK526776A (en) | 1977-05-25 |
FR2332294A1 (en) | 1977-06-17 |
AU501096B2 (en) | 1979-06-07 |
FR2332294B1 (en) | 1982-09-17 |
SE437154B (en) | 1985-02-11 |
IE43989L (en) | 1977-05-24 |
JPS5923301B2 (en) | 1984-06-01 |
AU1989676A (en) | 1978-06-01 |
IT1064475B (en) | 1985-02-18 |
BR7607847A (en) | 1977-10-25 |
ES453565A1 (en) | 1977-11-16 |
JPS5265248A (en) | 1977-05-30 |
CA1058853A (en) | 1979-07-24 |
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